Influence of the Methane-Zeolite A Interaction Potential on the Concentration Dependence of Self-diffusivity

Studies on the diffusion of methane in a zeolite structure type LTA (as per IZA nomenclature) have indicated that different types of methane zeolite potentials exist in the literature in which methane is treated within the united-atom model. One set of potentials, referred to as model A, has a methane oxygen diameter of 3.14 angstrom, while another set of potential parameters, model B, employs a larger value of 3.46 angstrom. Fritzsche and co-workers (1993) have shown that these two potentials lead to two distinctly different energetic barriers for the passage of methane through the eight-ring window in the cation-free form of zeolite A. Here, we compute the variation of the self-diffusivity (D) with loading (c) for these two types of potentials and show that this slight variation in the diameter changes the concentration dependence qualitatively: thus, D decreases monotonically with c for model A, while D increases and goes through a maximum before finally decreasing for model B. This effect and the surprising congruence of the diffusion coefficients for both models at high loadings is examined in detail at the molecular level. Simulations for different temperatures reveal the Arrhenius behaviour of the self-diffusion coefficient. The apparent activation energy is found to vary with the loading. We conclude that beside the cage-to-cage jumps, which are essential for the migration of the guest molecules, at high concentrations migration within the cage and guest guest interactions with other molecules become increasingly dominant influences on the diffusion coefficient and make the guest zeolite interaction less important for both model A and model B.

beta-Turn Analogues in Model a ss-Hybrid Peptides: Structural Characterization of Peptides Containing ss 2,2Ac6c and ss 3,3Ac6c Residues

The effect of gem-dialkyl substituents on the backbone conformations of beta-amino acid residues in peptides has been investigated by using four model peptides: Boc-Xxx-beta 2,2Ac6c(1-aminomethylcyclohexanecarboxylic acid)-NHMe (Xxx=Leu (1), Phe (2); Boc=tert-butyloxycarbonyl) and Boc-Xxx-beta 3,3Ac6c(1-aminocyclohexaneacetic acid)-NHMe (Xxx=Leu (3), Phe (4)). Tetrasubstituted carbon atoms restrict the ranges of stereochemically allowed conformations about flanking single bonds. The crystal structure of Boc-Leu-beta 2,2Ac6c-NHMe (1) established a C11 hydrogen-bonded turn in the a beta-hybrid sequence. The observed torsion angles (a(similar to-60 degrees, similar to-30 degrees), beta(similar to-90 degrees, similar to 60 degrees, similar to-90 degrees)) corresponded to a C11 helical turn, which was a backbone-expanded analogue of the type III beta turn in aa sequences. The crystal structure of the peptide Boc-Phe-beta 3,3Ac6c-NHMe (4) established a C11 hydrogen-bonded turn with distinctly different backbone torsion angles (a(similar to-60 degrees, similar to 120 degrees), beta(similar to 60 degrees, ?60 degrees, similar to-60 degrees)), which corresponded to a backbone-expanded analogue of the type II beta turn observed in aa sequences. In peptide 4, the two molecules in the asymmetric unit adopted backbone torsion angles of opposite signs. In one of the molecules, the Phe residue adopted an unfavorable backbone conformation, with the energetic penalty being offset by a favorable aromatic interaction between proximal molecules in the crystal. NMR spectroscopy studies provided evidence for the maintenance of folded structures in solution in these a beta-hybrid sequences.

Receive Antenna Selection for Time-Varying Channels Using Discrete Prolate Spheroidal Sequences

Receive antenna selection (AS) has been shown to maintain the diversity benefits of multiple antennas while potentially reducing hardware costs. However, the promised diversity gains of receive AS depend on the assumptions of perfect channel knowledge at the receiver and slowly time-varying fading. By explicitly accounting for practical constraints imposed by the next-generation wireless standards such as training, packetization and antenna switching time, we propose a single receive AS method for time-varying fading channels. The method exploits the low training overhead and accuracy possible from the use of discrete prolate spheroidal (DPS) sequences based reduced rank subspace projection techniques. It only requires knowledge of the Doppler bandwidth, and does not require detailed correlation knowledge. Closed-form expressions for the channel prediction and estimation error as well as symbol error probability (SEP) of M-ary phase-shift keying (MPSK) for symbol-by-symbol receive AS are also derived. It is shown that the proposed AS scheme, after accounting for the practical limitations mentioned above, outperforms the ideal conventional single-input single-output (SISO) system with perfect CSI and no AS at the receiver and AS with conventional estimation based on complex exponential basis functions.

Energy-efficient training for antenna selection in time-varying channels

Training for receive antenna selection (AS) differs from that for conventional multiple antenna systems because of the limited hardware usage inherent in AS. We analyze and optimize the performance of a novel energy-efficient training method tailored for receive AS. In it, the transmitter sends not only pilots that enable the selection process, but also an extra pilot that leads to accurate channel estimates for the selected antenna that actually receives data. For time-varying channels, we propose a novel antenna selection rule and prove that it minimizes the symbol error probability (SEP). We also derive closed-form expressions for the SEP of MPSK, and show that the considered training method is significantly more energy-efficient than the conventional AS training method.

Organophotocatalysis in nanostructured soft gel materials as tunable reaction vessels: comparison with homogeneous and micellar solutions

Riboflavin tetraacetate-catalyzed aerobic photooxidation of 1-(4-methoxyphenyl)ethanol was investigated as a model reaction under blue visible light in different soft gel materials, aiming to establish their potential as reaction vessels for photochemical transformations. Three strategies involving different degrees of organization of the catalyst within the gel network were explored, and the results compared to those obtained in homogeneous and micellar solutions. In general, physical entrapment of both the catalyst and the substrate under optimized concentrations into several hydrogel matrices (including low-molecular-weight and biopolymer-based gels) allowed the photooxidation with conversions between 55 and 100% within 120 min (TOF similar to 0.045-0.08 min(-1); k(obs) similar to 0.011-0.028 min(-1)), albeit with first-order rates ca. 1-3-fold lower than in solution under comparable non-stirred conditions. Remarkably, the organogel made of a cyclohexane-based bisamide gelator in CH3CN not only prevented the photodegradation of the catalyst but also afforded full conversion in less than 60 min (TOF similar to 0.167 min(-1); k(obs) similar to 0.073 min(-1)) without the need of additional proton transfer mediators (e. g., thiourea) as it occurs in CH3CN solutions. In general, the gelators could be recycled without detriment to their gelation ability and reaction rates. Moreover, kinetics could be fine-tuned according to the characteristics of the gel media. For instance, entangled fibrillar networks with relatively high mechanical strength were usually associated with lower reaction rates, whereas wrinkled laminated morphologies seemed to favor the reaction. In addition, the kinetics results showed in most cases a good correlation with the aeration efficiency of the gel media.

An estimate of equilibrium sensitivity of global terrestrial carbon cycle using NCAR CCSM4

Increasing concentrations of atmospheric CO2 influence climate, terrestrial biosphere productivity and ecosystem carbon storage through its radiative, physiological and fertilization effects. In this paper, we quantify these effects for a doubling of CO2 using a low resolution configuration of the coupled model NCAR CCSM4. In contrast to previous coupled climate-carbon modeling studies, we focus on the near-equilibrium response of the terrestrial carbon cycle. For a doubling of CO2, the radiative effect on the physical climate system causes global mean surface air temperature to increase by 2.14 K, whereas the physiological and fertilization on the land biosphere effects cause a warming of 0.22 K, suggesting that these later effects increase global warming by about 10 % as found in many recent studies. The CO2-fertilization leads to total ecosystem carbon gain of 371 Gt-C (28 %) while the radiative effect causes a loss of 131 Gt-C (10 %) indicating that climate warming damps the fertilization-induced carbon uptake over land. Our model-based estimate for the maximum potential terrestrial carbon uptake resulting from a doubling of atmospheric CO2 concentration (285-570 ppm) is only 242 Gt-C. This highlights the limited storage capacity of the terrestrial carbon reservoir. We also find that the terrestrial carbon storage sensitivity to changes in CO2 and temperature have been estimated to be lower in previous transient simulations because of lags in the climate-carbon system. Our model simulations indicate that the time scale of terrestrial carbon cycle response is greater than 500 years for CO2-fertilization and about 200 years for temperature perturbations. We also find that dynamic changes in vegetation amplify the terrestrial carbon storage sensitivity relative to a static vegetation case: because of changes in tree cover, changes in total ecosystem carbon for CO2-direct and climate effects are amplified by 88 and 72 %, respectively, in simulations with dynamic vegetation when compared to static vegetation simulations.

Advances in base- and mobile-station aided cooperative wireless communications : An overview

In recent years, there has been an upsurge of research interest in cooperative wireless communications in both academia and industry. This article presents a simple overview of the pivotal topics in both mobile station (MS)- and base station (BS)- assisted cooperation in the context of cellular radio systems. Owing to the ever-increasing amount of literature in this particular field, this article is by no means exhaustive, but is intended to serve as a roadmap by assembling a representative sample of recent results and to stimulate further research. The emphasis is initially on relay-base cooperation, relying on network coding, followed by the design of cross-layer cooperative protocols conceived for MS cooperation and the concept of coalition network element (CNE)-assisted BS cooperation. Then, a range of complexity and backhaul traffic reduction techniques that have been proposed for BS cooperation are reviewed. A more detailed discussion is provided in the context of MS cooperation concerning the pros and cons of dispensing with high-complexity, power-hungry channel estimation. Finally, generalized design guidelines, conceived for cooperative wireless communications, are presented.

Dynamics of the North American continent

The forces that cause deformation of western North America have been debated for decades. Recent studies, primarily based on analysis of crustal stresses in the western United States, have suggested that the deformation of the region is mainly controlled by gravitational potential energy (GPE) variations and boundary loads, with basal tractions due to mantle flow playing a relatively minor role. We address these issues by modelling the deviatoric stress field over western North America from a 3-D finite element mantle circulation model with lateral viscosity variations. Our approach takes into account the contribution from both topography and shallow lithosphere structure (GPE) as well as that from deeper mantle flow in one single model, as opposed to separate lithosphere and circulation models, as has been done so far. In addition to predicting the deviatoric stresses we also jointly fit the constraints of geoid, dynamic topography and plate motion both globally and over North America, in order to ensure that the forces that arise in our models are dynamically consistent. We examine the sensitivity of the dynamic models to different lateral viscosity variations. We find that circulation models that include upper mantle slabs yield a better fit to observed plate velocities. Our results indicate that a model of GPE variations coupled with mantle convection gives the best fit to the observational constraints. We argue that although GPE variations control a large part of the deformation of the western United States, deeper mantle tractions also play a significant role. The average deviatoric stress magnitudes in the western United States range 30-40 MPa. The cratonic region exhibits higher coupling to mantle flow than the rest of the continent. We find that a relatively strong San Andreas fault gives a better fit to the observational constraints, especially that of plate velocity in western North America.

Training for Antenna Selection in Time-Varying Channels: Optimal Selection, Energy Allocation, and Energy Efficiency Evaluation

Single receive antenna selection (AS) is a popular method for obtaining diversity benefits without the additional costs of multiple radio receiver chains. Since only one antenna receives at any time, the transmitter sends a pilot multiple times to enable the receiver to estimate the channel gains of its N antennas to the transmitter and select an antenna. In time-varying channels, the channel estimates of different antennas are outdated to different extents. We analyze the symbol error probability (SEP) in time-varying channels of the N-pilot and (N+1)-pilot AS training schemes. In the former, the transmitter sends one pilot for each receive antenna. In the latter, the transmitter sends one additional pilot that helps sample the channel fading process of the selected antenna twice. We present several new results about the SEP, optimal energy allocation across pilots and data, and optimal selection rule in time-varying channels for the two schemes. We show that due to the unique nature of AS, the (N+1)-pilot scheme, despite its longer training duration, is much more energy-efficient than the conventional N-pilot scheme. An extension to a practical scenario where all data symbols of a packet are received by the same antenna is also investigated.

Bipartite Powers of k-chordal Graphs

Let k be an integer and k >= 3. A graph G is k-chordal if G does not have an induced cycle of length greater than k. From the definition it is clear that 3-chordal graphs are precisely the class of chordal graphs. Duchet proved that, for every positive integer m, if G m is chordal then so is G(m+2). Brandst `` adt et al. in Andreas Brandsadt, Van Bang Le, and Thomas Szymczak. Duchet- type theorems for powers of HHD- free graphs. Discrete Mathematics, 177(1- 3): 9- 16, 1997.] showed that if G m is k - chordal, then so is G(m+2). Powering a bipartite graph does not preserve its bipartitedness. In order to preserve the bipartitedness of a bipartite graph while powering Chandran et al. introduced the notion of bipartite powering. This notion was introduced to aid their study of boxicity of chordal bipartite graphs. The m - th bipartite power G(m]) of a bipartite graph G is the bipartite graph obtained from G by adding edges (u; v) where d G (u; v) is odd and less than or equal to m. Note that G(m]) = G(m+1]) for each odd m. In this paper we show that, given a bipartite graph G, if G is k-chordal then so is G m], where k, m are positive integers with k >= 4

Antenna selection for time-varying channels based on slepian subspace projections

Single receive antenna selection (AS) allows single-input single-output (SISO) systems to retain the diversity benefits of multiple antennas with minimum hardware costs. We propose a single receive AS method for time-varying channels, in which practical limitations imposed by next-generation wireless standards such as training, packetization and antenna switching time are taken into account. The proposed method utilizes low-complexity subspace projection techniques spanned by discrete prolate spheroidal (DPS) sequences. It only uses Doppler bandwidth knowledge, and does not need detailed correlation knowledge. Results show that the proposed AS method outperforms ideal conventional SISO systems with perfect CSI but no AS at the receiver and AS using the conventional Fourier estimation/prediction method. A closed-form expression for the symbol error probability (SEP) of phase-shift keying (MPSK) with symbol-by-symbol receive AS is derived.

Mechanical and electronic properties of pristine and Ni-doped Si, Ge, and Sn sheets

Silicene, a graphene analogue of silicon, has been generating immense interest due to its potential for applications in miniaturized devices. Unlike planar graphene, silicene prefers a buckled structure. Here we explore the possibility of stabilizing the planar form of silicene by Ni doping using first principles density functional theory based calculations. It is found that planar as well as buckled structure is stable for Ni-doped silicene, but the buckled sheet has slightly lower total energy. The planar silicene sheet has unstable phonon modes. A comparative study of the mechanical properties reveals that the in-plane stiffness of both the pristine and the doped planar silicene is higher compared to that of the buckled silicene. This suggests that planar silicene is mechanically more robust. Electronic structure calculations of the planar and buckled Ni-doped silicene show that the energy bands at the Dirac point transform from linear behavior to parabolic dispersion. Furthermore, we extend our study to Ge and Sn sheets that are also stable and the trends of comparable mechanical stability of the planar and buckled phases remain the same.

Surface freshwater storage and variability in the Amazon basin from multi-satellite observations, 1993-2007

The amount of water stored and moving through the surface water bodies of large river basins (river, floodplains, wetlands) plays a major role in the global water and biochemical cycles and is a critical parameter for water resources management. However, the spatiotemporal variations of these freshwater reservoirs are still widely unknown at the global scale. Here, we propose a hypsographic curve approach to estimate surface freshwater storage variations over the Amazon basin combining surface water extent from a multi-satellite-technique with topographic data from the Global Digital Elevation Model (GDEM) from Advance Spaceborne Thermal Emission and Reflection Radiometer (ASTER). Monthly surface water storage variations for 1993-2007 are presented, showing a strong seasonal and interannual variability, and are evaluated against in situ river discharge and precipitation. The basin-scale mean annual amplitude of similar to 1200 km(3) is in the range of previous estimates and contributes to about half of the Gravity Recovery And Climate Experiment (GRACE) total water storage variations. For the first time, we map the surface water volume anomaly during the extreme droughts of 1997 (October-November) and 2005 (September-October) and found that during these dry events the water stored in the river and floodplains of the Amazon basin was, respectively, similar to 230 (similar to 40%) and 210 (similar to 50%) km(3) below the 1993-2007 average. This new 15 year data set of surface water volume represents an unprecedented source of information for future hydrological or climate modeling of the Amazon. It is also a first step toward the development of such database at the global scale.

Simulation of inhomogeneous distributions of ultracold atoms in an optical lattice via a massively parallel implementation of nonequilibrium strong-coupling perturbation theory

We present a nonequilibrium strong-coupling approach to inhomogeneous systems of ultracold atoms in optical lattices. We demonstrate its application to the Mott-insulating phase of a two-dimensional Fermi-Hubbard model in the presence of a trap potential. Since the theory is formulated self-consistently, the numerical implementation relies on a massively parallel evaluation of the self-energy and the Green's function at each lattice site, employing thousands of CPUs. While the computation of the self-energy is straightforward to parallelize, the evaluation of the Green's function requires the inversion of a large sparse 10(d) x 10(d) matrix, with d > 6. As a crucial ingredient, our solution heavily relies on the smallness of the hopping as compared to the interaction strength and yields a widely scalable realization of a rapidly converging iterative algorithm which evaluates all elements of the Green's function. Results are validated by comparing with the homogeneous case via the local-density approximation. These calculations also show that the local-density approximation is valid in nonequilibrium setups without mass transport.

Theoretical description of coherent doublon creation via lattice modulation spectroscopy

Using a recently developed strong-coupling method, we present a comprehensive theory for doublon production processes in modulation spectroscopy of a three-dimensional system of ultracold fermionic atoms in an optical lattice with a trap. The theoretical predictions compare well to the experimental time traces of doublon production. For experimentally feasible conditions, we provide a quantitative prediction for the presence of a nonlinear ``two-photon'' excitation at strong modulation amplitudes.